Fluoro compounds and synthesis thereof



United States Patent 3,374,273 FLUORO COMPOUNDS AND SYNTHESIS THEREOF William J. Cunningham, Somerset, and Cyril Woolf, Morris Township, Morris County, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 297,220, July 24, 1963. This application Oct. 31, 1966, Ser. No. 591,034

4 Claims. (Cl. 260-693) This application is a continuation-in-part of our copending application, Ser. No. 297,220, filed July 24, 1963, now abandoned which latter application is, in turn, a continuation-in-part application of our copending application Ser. No. 263,430, filed Mar. 7, 1963, now abandoned.

This invention relates to the monohydrate of CF COCF C1 and to a process for converting monohydrates of both CF COCF Cl and CF COCF to constant boiling compositions of these fluorinated ketones with water, corresponding to CF COCF Cl-3H O and CF COCE -3H O, respectively.

Hexafiuoroacetone, CF COCF is a known compound made by known processes, and is of known utility, e.g., it has been used to prepare the hexafluoro-bisphenol A compound which has been converted to fluorine-containing polycarbonate resin. Likewise, pentafluorochloroacetone is a known compound made by known processes, and is of known utility such as when hydrolyzed by treatment with strong alkali at moderately low temperatures yields the alkali metal salt of trifluoroacetic acid which when acidified with sulfuric acid produces CF COOH, a commercial product.

Under normal conditions, CF COCF is a gaseous compound having a boiling point of minus 27 C. and a melting point of about minus 129 C., and CF COCF Cl is a gaseous compound having a boiling point of plus 8 C. and a melting point of minus 133 C. Storage and shipment of CF COCF CI and CF COCF may be made, as is, with compressed gas equipment, or, as will be described in more detail hereafter, as solid or liquid hydrate, in which form they are more easily handleable.

An object of this invention is to provide a solid hydrate form of CFgCOCFgCl.

Another object of the invention is to provide a method for converting the solid monohydrates of CF C0CF Cl and CF COCF to liquid, constant boiling compositions corresponding to CF COCF Cl-3H O and respectively.

Other objects and advantages of the invention will become apparent from the following description.

CF COCF -3H O is a constant boiling, water-white liquid at atmospheric pressure, boiling at about 105 C. It has been reported in the literature as a hydrate of CF C0CF A. T. Morse et al. in Canadian Journal of Chemistry, vol. 33, No. 3 (March 1955), p. 456', disclose it as hexafluoroacetone hydrate, B.P. 55-6" C. at 80 mm. Chemical Abstracts, vol. 54 (1960), 2084111, discloses it as perfiuoroacetone hydrate, b 50. Henne et al., in Journal of the American Chemical Society, vol.

72 (1950), p. 3578, disclose it as CF COCF hydrate, B.P. 57 at 93 mm.

Strictly speaking, a hydrate is a true compound. The art has, however, used this term loosely to describe compositions which are not true compounds but which behave in some respects as true compounds, such as bv exhibiting a constant boiling point.

CF COCF '3H O exhibits many properties characteristic of a true compound. Recent study of the freezing characteristics of this composition has, however, indicated that CF COCF -3H O is in fact not a true compound but is a constant boiling distillable mixture satisfying the empirical formula CF COCF -3H O. To facilitate expression and to be consistent with the prior art terminology for the constant boiling mixture of CF COCF and three (3) moles of H 0, this composition will be referred to herein as a hydrate and, more particularly, as the trihydrate 0f CF COCF Cl-3H O is a constant boiling, Water-white liquid at atmospheric pressure, boiling at about C. and also will be referred to as a hydrate.

In the forms of the trihydrates, each of CF COCF Cl and CF COCF may be stored, shipped, piped, pumped and otherwise handled as conveniently as water. At the point of ultimate use each of the fluorinated ketones may be recovered in substantially pure form from the trihydrates by economical procedures. Further, each of these fluorinated ketones may be converted to the corresponding monohydrate by conveniently practicable procedure. The CF COCF -H O is a white crystalline solid having a melting point of about 40 C., and the is a similar white crystalline solid having a melting point of 26.0-26.5 C. In the forms of the solids, the ketones may be stored and shipped in conventional containers. As described below, at point of use, each of the ketones may be recovered in substantially pure form from the monohydrates.

In the following specification and claims, the terms fiuorinated ketone, ketone and FK, unless otherwise modified, define material selected from the group consisting of CF COCF Cl and CF COCF The FK hydrates may be prepared by contacting, preferably as sole reactants, FK with liquid-phase water in amount equivalent to at least one mol of H 0 per mol of FK, while in a reaction medium preferably consisting of PK and water, and while maintaining temperatures such that any free water present is in liquid phase, and recovering from the resulting reaction mass FK. xH O where x is a whole odd number from one to 3, specific manner of hydrate recovery being dependent largely upon the relative amounts of PK and water in any given reaction medium or other liquor, and upon the specific sought-for product.

FK-H O may be prepared by introducing the required amount of FK into the amount of water required to form the monohydrate. When FK is introduced into liquid water, reaction between PK and H 0 takes place and continues until the amount of FK charged is slightly more than equivalent to about one mol proportion of FK per mol of H 0 charged. Thereafter any further quantity of FK introduced passes off as an unreacted gas. At this stage, if reaction temperature is held appreciably below about the melting point of the FK-H O (about 40 C. in the case of CF COCF -H O and about 26.026.5 C. in the case of CF COCF Cl) there is formed in the contacting vessel a somewhat moist but relatively solid mass of relatively long, needle-like crystals of FK monohydrate. Reaction temperature may be controlled by regulation of rate of introduction of FK into the water or by other suitable means. The FK-H O material, thus produced, is sufficiently pure for the purposes of storage and shipping. If a more purified product is desired, the material may be gently heated just below or about its melting point to dry off the slight excess of ketone. At a point of ultimate use, the solid FK-H O may be dehydrated to pure FK with a desiccant such as conc. H 80 or P or it may be added to enough water to form the corresponding liquid FK-3H O which in turn may be dehydrated, if desired, in a similar fashion to recover corresponding pure FK.

According to the invent-ion process, it has been found that FK-3H O may be formed from a mass containing PK and less than a 3:1 proportion of water to FK. This phase of the invention is based on the facts that FK-3H O boils constantly at about 105 C., and that FK, on heating, disassociates to PK and FK-3I-I O in accordance with In accordance with the invention, FK-3H O may be recovered from substantially solid and/ or liquid FK-H O. To effect recovery of FK-3H O, the FK'H O may be placed in an ordinary heating pot or vessel. On applica* tion of heat to the pot, the FK-H O, if initially solid, melts. On further heating and raising of temperature, PE is evolved, and on continued heating at temperature and for a time interval enough to vaporize all constituents boiling at temperature below about 105 C., there remains in the pot a solution constantly boiling at about 105 C. and consisting of liquid FK'3H O.

The following illustrate practice of the invention.

EXAMPLE 1 Apparatus employed included a single-necked flask provided with a magnetic stirrer, and at the top of the neck with a Dry Ice-acetone cold finger. Incoming reactants charged consisted of water and CF COCF About 92.5 g. (5.144 m.) of water were introduced into the flask. With constant stirring of flask contents, vaporous CF COCF was fed into the cold finger in which condensed and then dropped as liquid into the water. During a period of about 6 hrs., about 577 g. (3.48 m.) of CF COCF were thus fed into the flask, and were absorbed in the water. During addition of the CF COCF the contents of the flask warmed up to about 40 C. At this stage, the flask contained about 680 g. of liquid material, and mol ratio of CF COCF to H O of such material was about 1:1.48. The contents of the flask were split into two approximately equal increments each containing about 1.74 m. of CF COCF and about 2.57 m. of H 0. To a first increment of about 344 g. in a suit able flask equipped with a cold finger, an additional 157 g. (0.95 m.) of CF COCF were added in the manner described above, at which point no more CF COCF was absorbed. Temperature in the flask was about -30 C. Contents of the flask comprised a slightly moist mass composed of long, needle-like white solid crystals containing CF COCF and H 0 constituents in mol ratio of about 2.69 to about 2.57, and having a melting point of about 40 C., and constituting the monohydrate CF COCF H O The neck of the flask was connected to a distillation column having a cooled head. On heating the contents of the flask gradually up to a pot temperature a little below about 105 C., the solids melted at about 40 C. and there was distilled over a gas which, when condensed in a Dry Ice trap, amounted to about 196 g. (1.18 m.) of water white liquid. The gas discharged from the distillation column during distillation was subjected to infrared analysis which showed the C=O group and otherwise the known pattern of CF COCF Condensate, resulting from cooling of the gas, was distilled in a separate operation and found to have the minus 27 C. B.P. of anhydrous CF COCF When discharge of gas, identified to be CF COCF from the top of the distillation column ceased, the latter was put on reflux maintained at C. On take-oif of product from the column, temperature including pot temperature remained at about 105 C. over the entire distillation operation to a substantially dry and empty pot. During distillation there was produced an off-gas which when condensed at about room temperature amounted to about 146 g. (0.65 m.) of water white liquid. The latter was analyzed by nuclear magnetic resonance and was found to contain 52.95% (by weight) of fluorine and 2.68% of hydrogen, corresponding theoretical values for CF COCF -3H O being 51.8% and 2.73%. The found values indicate about 71.1% hexafluoroacetone and 24.1% H O as compared with theory values of about 75.5% and 24.5% respectively. In the formula x calculated on the basis of hydrogen analytical result equals 2.92 m.,and x calculated on the basis of the fluorine result equals 2.73 m. Infrared absorption spectrum showed the presence of fluorine atoms and the presence of hydroxyl group. Phase studies of this material showed that it was not a true compound, but a constant boiling composition corresponding to CF COCF -3H O. Hexafluoroacetone was quantitatively recovered from this composition by distilling a sample of the product in the presence of concentrated sulfuric acid. Accordingly, on heating the substantially solid crystalline monohydrate, CF COCF -H O, disassociated to CF COCF and CF COCF 3H O Under normal conditions the latter is a water-white liquid having a constant boiling point of about 105 C. and a specific gravity at 25 C. of about 1.6.

EXAMPLE 2 About g. of CF COCF Cl were condensed into a flask cooled in a Dry Ice-acetone slush. About 18 g. of water were added gradually to the CF COCF Cl. On completion of water addition, during which temperature was a little above zero, there was formed in the flask a slightly moist mass composed of white solid crystals containing CF COCF Cl and H 0 constituents in mol ratio of 1.07 to one, i.e., corresponding substantially to the monohydrate, CF COCF Cl'H O. This material was found to have a melting point of 26.026.5 C. The neck of the flask was connected to a distillation column having a cooled head. On heating up the flask contents to a little below about 105 C., the solids melted at a little above 26-27 C., and there was distilled over a gas which, when condensed in a Dry-Ice trap amounted to about 112 g. of water-white liquid. Infrared analysis of the latter showed the C=O group and otherwise known pattern of CF COCF CI, and the material boiled at the plus 8 C. B.P. of anhydrous CF COCF Cl. When discharge of gas from the top of the distillation column ceased, the latter was put on reflux maintained at about 105106 C. On take-ofl? of further vaporous product from the column, temperature including pot temperature remained at about 105-106 C. during distillation to a substantially dry and empty pot. In the course of distillation, there was produced an off-gas which, when condensed to about room temperature, amounted to about 81 g. of water-white liquid. On the basis that initial addition of water to the CF COCF CI formed CF COCF Cl-H O, and that during heating and distillation of the solid material the CF COCF Cl-H O was disassociated to CF COCF Cl and CF COCF Cl-3H O, recovery of 112 g. of CF COCF C1 compares with theoretical 121 g. recovery of indicating a ketone loss. On basis of the water charged, the 105-106 C. constant boiling liquor corresponded to CF COCF CI'28H O. Instrumental NMR analysis of the constant boiling liquor for fluorine showed 39.8% by Weight as compared with the 40.2% theory for Based on material balance, fluorine analysis, and phase studies, the final condensate was established not to be a true compound but a constant boiling composition corresponding to CF COCF Cl-3H O. The composition has a specific gravity at 25 C. of about 1.63.

EXAMPLE 3.

About 23.5 g. (0.1 m.) of CF COCF Cl-3H O, B.P. 105 C., prepared as described in Example 2, were introduced into a flask cooled in Wet ice. About 41 g. (0.23 m.) of gaseous CF COCF CI were bubbled into the liquid trihydrate. On cessation of feed of CF COCF CI, the contents of the flask comprised a slightly moist mass containing CF COCF CI and H 0 constituents in mol ratio of 0.33:0.30. The resulting mass was heated gently at less than about 30 C., and there were vaporized off and recovered about 7.5 g. of material identified by infrared to be CF COCF CI. The residue recovered in the flask was a relatively dry white crystalline solid material in amount of 5 7 g. corresponding to about 60 g. of

theoretically recoverable as CF COCF Cl-H O. Melting point of the solid material was determined to be about 26.5 C. Infrared absorption spectrum analysis showed the presence of fluorine atoms and the presence of a relatively narrow 0.1 micron hydroxyl absorption in the 3 micron range. The material absorbs at 9.4 microns as compared with the 9.24 microns of the three water hydrate of Examples 3-5. Infrared analysis, material balance and phase studies establish the product to be CF COCF Cl H 0 We claim: 1. The process for making a hydrate selected from the group consisting of CF COCF 3H O and CF COCF Cl-3H O CF COCF 3H O is prepared by heating CF COCF -H O.

3. The process according to claim 1 in which is prepared by heating CF COCF Cl'H O.

4. The normally solid compound represented by the formula CF COCF Cl-H O having a melting point of about 26.026.5 C.

References Cited UNITED STATES PATENTS 2,617,836 11/1952 Pearlson et al 260-5935 2,870,211 1/1959 Miller et al 260593.5

DANIEL D. HORWITZ, Primary Examiner. 

1. THE PROCESS FOR MAKING A HYDRATE SELECTED FROM THE GROUP CONSISTING OF CF3COCF3$3H2O AND 